Novel N-3-aminoalkyl amides, polymers thereof, and method for their preparation

ABSTRACT

N-3-Aminoalkyl propionamides with an ether substituent on the beta carbon atom are prepared by the reaction of analogous N-3oxohydrocarbon-substituted amides with an amine in the presence of a reducing agent, preferably hydrogen and a hydrogenation catalyst. The resulting compounds can be converted to acrylamides by pyrolysis in the presence of a strong base. The latter compounds may also be prepared by the reaction of an Alpha , Beta -unsaturated amine with an acrylonitrile in the presence of sulfuric acid. They are useful for improving dyeability of fiberforming polymers and may be polymerized to form compositions which improve paper strength and (in their quaternized form) are excellent flocculants.

United States Patent Hoke May 13, 1975 [54] NOVEL N-3-AMINOALKYL AMIDES,3,661,880 5/1972 Markert 260/895 N AND METHOD FOR FOREIGN PATENTS ORAPPLICATIONS 790,563 2/1958 United Kingdom 260/89.7 N [75] Inventor:Donald 1. Hoke, Chagrin Falls, 01110 [73] Assignee: The LubrizolCorporation, Primary Examiner-Harry Wong, Jr.

Cleveland, Ohio Attorney, Agent, or Firm-James W. Adams, Jr.; 221 Filed:Dec. 1, 1971 Wlham [21] Appl. No.1 203,853

[57] ABSTRACT Related U.S. Application Data [62] Division of Ser. No 832412 June 11 1969 Pat. No. N'3'Ammoalkyl proponamdes an ether substtu' 3666 810 ent on the beta carbon atom are prepared by the reaction ofanalogous N-3-oxohydrocarbon-substituted 52 U.S. Cl 260/855 R- 8/162'162/168- amides with an amine in WmCe of a reducing 26O/2 2 260/63260/785 260/803 agent, preferably hydrogen and a hydrogenation cata-260/82 260/851: 260/861 260/875 lyst. The resulting compounds can beconverted to ac- 1 260/88 3 260/89'7 rylamides by pyrolysis in thepresence of a strong 260/561 Q base. The latter compounds may also beprepared by 51 Int. Cl. C08f 3/90- C08f 15/02 the heactiOh ahafi'uhsaturated amine with [581 Field of S h 260/793 MU 7 N 803 Nlonitrile in the presence of sulfuric acid. They are use- 260/855 A 861ful for improving dyeability of fiber-forming polymers and may bepolymerized to form compositions which [56] References Cited improvepaper strength and (in their quaternized form) are excellentflocculants.

8 Claims, No Drawings i 1 NOVEL N-S-AMINOALKYL AMIDES, POLYMERS THEREOF,AND METHOD FOR THEIR PREPARATION This is a division of application Ser.No. 832,412 filed June 11, 1969, now U.S. Pat. No. 3,666,810.

This invention relates to new compositions of matter, both monomeric andpolymeric, and methods for their preparation. More particularly, itrelates to compounds of the formula W i R -CH-C-C-N-C-R I'll RSRSH R ishydrogen or a lower alkyl radical; R is a hydrocarbon radical; Y is X isa salt-forming anion; Z is hydrogen or a hydrocaris a heterocyclicradical; and Z is hydrogen or a lower alkyl radical.

As used herein, the term hydrocarbon radical" includes alkyl,cycloalkyl, aryl, aralkyl and alkaryl radicals. It also includessubstantially hydrocarbon radicals; that is, radicals which containsubstituents such as ether, ester, nitro or halogen provided suchsubstituents do not materially alter the character or reactivity of theradicals. The term lower alkyl radical denotes alkyl radicals containingno more than about 10 carbon atoms.

In the preferred embodiments of the compounds of this invention, each ofR is a hydrogen, lower alkyl, or C aromatic radical; each of R and R isa lower alkyl, C cycloalkyl or C aromatic radical; R is hydrogen ormethyl; R is a lower alkyl or C aromatic radical; Z and Z are loweralkyl or C cycloal kyl radicals, or

is a heterocyclic radical such as pyrrolidino, piperidino or morpholino;and X (if present) is any typical saltforming anion such as chloride,bromide, iodide, sulfate, bisulfate, acetate, carbonate, bicarbonate orthe 30 like. More desirably, each of R is hydrogen or lower alkyl, eachof R and R is lower alkyl, R is hydrogen, R is lower alkyl, Z and Z arelower alkyl, and Z (if present) is methyl.

The following are illustrative of the compounds of bon radical and Z ishydrogen or an alkyl or cycloalkyl 35 this invention.

radical, or

' N-( 1, l dime thyl-B-dime thylaminopropyl) acrylamide CH H N-( l,l-dimethyl-E-dime tliylaminobutyl) aerylamide Dime thyl-3-(l-aczylamido-l, l-dime thylpropyl) ammonium chloride CH3 0 l l Compoundsof the present invention wherein R is -CHCH2OR (hereinafter sometimesreferred to as oxy com pounds) may be prepared by reacting anoxypropionamide of the formula R2R4 o 1 1 ,R -C-C-C-N-C-CHCH OR RRH R7with an amine of the formula is of the type generally identified asreductive amination. A typical example of such a reaction is theLeuckart reaction, in which an oxo compound is reacted with an amine inthe presence of formic acid, or with an amine formate, with the resultthat the carbon atom formerly part of the 0x0 group is aminated andcarbon dioxide and water are evolved as by-products.

A preferred method for reductive amination of the oxypropionamideinvolves its reaction with the amine in the presence of hydrogen and ahydrogenation catalyst such as platinum/platinum oxide, palladium,copper chromite or Raney nickel. Of these catalysts, platinum/platinumoxide Adams catalyst) is preferred. (It is referred to asplatinum/platinum oxide because it is usually introduced as the oxide,but is immediately reduced to elemental platinum upon contact withhydrogen.) Typically, the oxypropionamide and the amine are mixed and asmall amount of the hydrogena tion catalyst is added; the mixture isthen pressurized with hydrogen to at least about 50 psi. and agitated,typically at a temperature of about 25100C. and usually with periodicreplenishment of the hydrogen pressure, until hydrogen uptake hasceased. The reductive amination may be effected in the presence of asuitable solvent such as an alcohol, ether or the like, but such solventis frequently unnecessary. It has also been found that the presence of asmall amount (usually about 0.1-5.0% by weight of the reaction mixture)of an acid increases the reaction rate. Typical acids which may be usedare aromatic sulfonic acids, mineral acids, perchloric acid and aminesalts thereof, and the like.

The molar ratio of amine to oxypropionamide in the reaction mixtureshould be at least 1:1, and is generally greater (up to about :1).Ratios between about 1.25:1 and 3:1 are preferred.

Following completion of the reductive amination re action, the productmay be isolated and purified in the customary ways.

The following examples illustrate the preparation of oxy compounds ofthe present invention. All parts, percentages and proportions are byweight unless otherwise stated.

EXAMPLE 1 To a mixture of 201 parts (1 mole) of N-( 1,1-dimethyl-3-oxobutyl)-3-methoxypropionamide and 91 parts (2 moles) ofdimethylamine are added 0.5 part of platinum oxide and 3 parts ofp-toluenesulfonic acid. The liquid mixture is poured into ahydrogenation bottle, flushed with hydrogen and pressurized withhydrogen on a Parr hydrogenation apparatus at 69 psi. and hydrogenatedfor about 12 hours, with hydrogen pres sure being replenished to 70 psi.when it has dropped to 27 psi. The mixture is then stripped on a rotaryevaporator and the residue, a yellow liquid, is dissolved in 16% aqueoushydrochloric acid and extracted with four 100-ml. portions ofchloroform. The aqueous solution is then made alkaline by the additionof a solution of 30 parts of sodium hydroxide in 75 parts of water, thealkaline solution is again extracted with four 100-m1. portions ofchloroform and the chloroform extracts are stripped and distilled. Thedesired product, N-( 1,1-dimethyl-3-dimethylaminobutyl)-3methoxypropionamide, is obtained boilingat 87-95C./0.5 mm. It contains 12.1% nitrogen, as compared with 12.2%theoretical.

EXAMPLE 2 pionamide is reacted with 95 parts (2.1 1 moles) ofdimethylamine in the presence of 1.75 parts of aqueous perchloric acidand 0.5 part of platinum oxide. The product is N-( 1, l -dimethy1-3-dimethylaminobutyl)-3-phenoxypropionarnide.

EXAMPLE 3 The procedure of Example 2 is repeated, except that thephenoxypropionamide used therein is replaced by 216 parts (1 mole) ofN(l,l-dimethyl-3-oxobutyl)-3- methoxy-l-methylpropionamide. The productis N- (1,1-dimethyl-3-dimethy]aminobutyl)-3-methoxy-1-methylpropionamide.

EXAMPLE 4 A one-gallon autoclave, fitted with a stirrer, is charged with1684 parts (8.38 moles) of N-(l,1-dimethyl-3-oxobutyl)-3-methoxypropionamide, 762 parts 16.9 moles) ofdimethylamine, 1.5 parts of platinum oxide and 15 parts ofdimethylammonium perchlorate. The autoclave is pressurized with hydrogento 750 psi., and stirring is begun. Hydrogen pressure is periodicallyrestored to 850900 psi. and stirring is continued until hydrogen uptakehas ceased. Sodium bicarbonate, 10 parts, is added to the mixture whichis then stripped, acidified, extracted with chloroform, made alkalineand again extracted with chloroform as in Example 1. The chloroformextract from the alkaline solution is stripped and distilled, and theproduct, N-( 1,1- dimethyl-3-dimethylaminobutyl)-3-methoxypropionamide,is obtained boiling at lO8C./O.9 mm. The yield is 1418.6 parts, or 73.6%of the theoretical amount.

EXAMPLE 5 The procedure of Example 4 is repeated, except that themethoxypropionamide used therein is replaced by 325 parts (1 mole) ofN(1,3-diphenyl-l-methy]-3- oxopropyl)-3-methoxypropionamide. The productis N-(1,3-diphenyl-lmethyl-3-dimethylaminobutyl)-3- methoxypropionamide.

EXAMPLE 6 EXAMPLE 7 Following the procedure of Example 4, a mixture of201 parts (1 mole) of N-(l,l-dimethyl-B-oxobutyl)-3-methoxypropionamide, 170 parts (2 moles) of piperidine, 0.5 part ofplatinum oxide and l part of dimethylammonium perchlorate ishydrogenated in the Parr apparatus, starting at a pressure of 70 psi.and recharging when the pressure has reached 39 psi. After workup asdescribed in Example 4, the desired product, N-( 1.1-dimethyl-3-piperidinobutyl)-3-methoxypropionamide, is obtained boilingat ll2l lC./0.25 mm.

EXAMPLE 8 Following the procedure of Example 1, 20.1 grams (0.1 mole) ofN-( 1, l-dimethyl-3-oxobutyl)-3-methoxypropionamide is reacted withgrams (0.14 mole) of pyrrolidine in the presence of 0.3 gram of platinumoxide and 100 ml. of methanol. When hydrogen uptake has ceased, themethanol is stripped and the product, N-( l l-dimethyl-3-pyrrolidylbutyl )-3-methoxypropionamide, is isolated asdescribed in Example 1.

EXAMPLE 9 Following the procedure of Example 1,N-(1,ldimethyl-3-morpholinobutyl)-3-methoxypropionamide is prepared bythe reaction of 201 parts 1 mole) of N- l,1-dimethyl-3-oxobutyl)-3-methoxypropionamide with 174 parts (2 moles)of morpholine in the presence of 0.5 part of platinum oxide and 1 partof dimethylammonium perchlorate.

EXAMPLE 10 The procedure of Example 4 is repeated, except that thedimethylamine is replaced by 1810 parts (16.9 moles) of methylaniline.The product isN-(1,ldimethyl-3-methylanilinobutyl)-3-methoxypropionamide.

The compounds of this invention wherein R is (hereinafter sometimesreferred to as acrylamido compounds) may be obtained from the oxycompounds described above by elimination of R OH by any of severalmethods which are known per sc. Typical methods are described briefly ina recent review: P. F.

Butskus et al., Russian Chemical Reviews, 35, 39

(1966). The preferred method is pyrolysis in the presence of a basicreagent, ordinarily a strong base such as solid sodium hydroxide, atabout 70150C. This reaction is conveniently carried out at reducedpressure.

Another method for preparation of acrylamido compounds of this inventionis by the reaction of a nitrile of the formula with an a,B-unsaturatedamine of the formula in the presence of sulfuric acid. Unsaturatedamines of this type may be prepared by the reaction of a compound of theformula with a 1,3-diene, usually in the presence of a strongly alkalinecatalyst such as metallic sodium. This is a typical 1,4-additionreaction, known in the art.

For the reaction of the unsaturated amine with the nitrile, it isusually preferred to use at least about 1.5 moles, typically about1.9-3.0 moles, of the nitrile per mole of unsaturated amine. Thesulfuric acid should be at least about 90%, and preferably 96-98%, instrength and the molar ratio of sulfuric acid to amine should be atleast about 1:1, and preferably between about 1.111 and 2:1. Solventsare usually unnecessary, but it may be advantageous to add a smallamount of a polymerization inhibitor such as hydroquinone, a hinderedphenol or the like. When the reaction is complete, the product may beisolated by diluting and neutralizing the mixture and separating theunsaturated amide by traditional techniques.

The preparation of acrylamido compounds of this invention is illustratedby the following examples.

EXAMPLE 1 l A mixture of 144.7 parts (0.63 mole) of N-(1,1-dimethyl-3-dimethylaminobutyl)-3-methoxypropionamide, 1 part of solidsodium hydroxide and 1 part of hydroquinone is charged to a reactionflask fitted with a condenser with a Dry Ice-cooled receiver, a stirrerand temperature control means. The pressure in the flask is reduced toless than 5 mm. and the flask is heated to 80C. Vigorous reaction beginsand liquid condenses in EXAMPLES 12-14 The procedure of Example 11 isrepeated starting with, respectively, N -(1,3-diphenyl-l-methyl-3-dimethylaminopropyl)-3-methoxypropionamide, N-(l,1-dimethyl3-piperidinobutyl)-3-methoxypropionamide, and N-(l,ldimethyl-3methylanilinobutyl)-3- methoxypropionamide. Thecorresponding acrylamides are obtained.

EXAMPLE 15 To a mixture of 273 parts (4 moles) of isoprene and 2 parts(0.087 mole) of sodium metal, at C., is added 180 parts (4 moles) ofdimethylamine over 1 hour. The temperature is maintained below 12C. bycooling with a Dry lce-isopropanol-filled cooling coil. After thedimethylamine addition is complete, the mixture is stirred and cooledfor an additional 3% hours. Metha no], 6 parts, is then added todecompose the sodium and the mixture is distilled. The fraction boilingat ll7.5119.5C. is the desired l-dimethylamino-3- methyl-2-butene.

A resin flask is cooled to 0C. and 450 grams (8.5 moles) ofacrylonitrile, 1020 grams 10 moles) of sulfuric acid and 37 grams ofwater are added. To this mixture are then added 475 grams (4.2 moles) ofthe ldimethylamino-3-methyl-2-butene prepared as described above, and8.5 grams of 2,6-di-t-butyl-p-cresol. t

The mixture is stirred at 68C. for about 1 hour and is then neutralizedwith about 30% sodium hydroxide. The organic layer is separated, dilutedwith 2050 ml. of methanol and neutralized with ammonia. An additional1000 ml. of methanol is added and the solution is filtered. The methanolis stripped from the filtrate and the residue is distilled. There isobtained 400 grams (64.5% of the theoretical amount) of the desired N-l, l -dimethyl-3-dimethylaminopropyl )acrylamide boiling at75-92C./O.250.9 mm. The nitrogen analysis is 15.4%, as compared with atheoretical value of 15.2%.

The amino compounds prepared as described above may be converted intoamine salts by reaction with a suitable acid, or into quaternaryammonium salts by reaction with an alkyl halide, sulfate or the like.This is illustrated in the following examples.

EXAMPLE 16 Methyl iodide, 2.8 grams (0.0197 mole), is added to asolution of 3.6 grams (0.0182 mole) ofN-(l,ldimethyl-3-dimethylaminobutyl)acrylamide in 10 ml. of benzene. Anexothermic reaction takes place and the temperature of the mixture isheld at 2530C. by external cooling. Upon stirring overnight, a gummysolid precipitates; this solid is separated and recrystal ized from amixture of methanol and benzene. There is obtained 4.7 grams of thedesired trimethyl3-( 1- acrylamido-1,l-dimethylbutyl)ammonium iodide.

EXAMPLE 17 Hydrogen chloride is bubbled through a solution of grams ofN-( l ,l-dimethyl-3-dimethylaminopropyl)acrylamide in benzene. Thedesired dimethyl-3-( lacrylamido-l l -dimethylpropyl )ammonium chlorideprecipitates and is separated by filtration.

The oxy compounds of this invention are useful primarily as chemicalintermediates for the preparation of acrylamido compounds, as describedhereinabove.

The acrylamido compounds of this invention are readily polymerized,either alone or with other monomars. The term polymer, as used herein,includes homopolymers, copolymers, terpolymers and other interpolymers.

The free-radical method is generally the most come 5 nient one forpolymerization of the compounds of this invention. Polymerization bythis method may be effected in bulk, solution, suspension or emulsion,by contacting the monomer or monomers with a polymerization initiatoreither in the absence or presence of a diluent at a temperature of aboutO200C. Suitable free-radical initiators include benzoyl peroxide,tertiary butyl hydroperoxide, acetyl peroxide, hydrogen peroxide,azobisisobutyronitrile, sodium persulfate, ammonium persulfate-sodiummetabisulfite, chlorate-sulfite and the like. Solution polymerizationmay be effected in an organic solvent such as benzene, toluene,cyclohexane, n-hexane, naphtha, tetrahydrofuran, mineral oil or thelike; emulsion and suspension polymerization are conveniently effectedin water or a mixture of water with a hydroxylated organic solvent.

Free-radical polymerization of the monomers of this invention may alsobe effected by photoinitiation techniques using ultraviolet, visible orinfrared radiation. For these methods, the presence of suitableinitiators and sensitizers, which are known in the art, is required.

Suitable emulsifiers for use in the preparation of emulsion polymers ofthis invention include cationic materials'such as stearyl dimethylbenzyl ammonium chloride; non-ionic materials such as alkyl arylpolyether alcohols and sorbitan mono-oleate; anionic materials such assodium decylbenzene sulfonate, dioctyl sodium sulfosuccinate, sodiumsalts of alkyl aryl polyether sulfates, and sodium lauryl sulfate;alkali metal salts of lignosulfonic acids, silicic acids and the like;35 and colloidal materials such as casein, sodium polyacrylate,carboxymethylcellulose, hydroxyethylcellulose, gum tragacanth, sodiumalginate, gelatin, methylcellulose, gum arabic, dextrins or polyvinylalcohol. A large variety of monomers can be used to form interpolymerswith the compounds of this invention. For the most part, these monomersare polymerizable vinyl compounds. They include (1) esters ofunsaturated alcohols, (2) esters of unsaturated acids, (3) esters ofunsaturated polyhydric alcohols (e.g., butenediol), (4) vinyl cycliccompounds, (5) unsaturated ethers, (6) unsaturated ketones, (7)unsaturated amides, (8) unsaturated aliphatic hydrocarbons, (9) vinylhalides, (10) unsaturated acids, (11) unsaturated acid anhydrides, (l2)unsaturated acid chlorides, and (13) unsaturated nitriles. Specificillustrations of such compounds are:

1. Esters of unsaturated alcohols: Allyl, methallyl, crotyl,l-chloroallyl, 2-chloroallyl, cinnamyl, vinyl, methylvinyl, l-phenallyl,butenyl esters of(a) saturated acids such as acetic, propionic, butyric,valeric, caproic and stearic; (b) unsaturated acids such as acrylic,alpha-substituted acrylic (including alkylacrylic, e.g., methacrylic,ethylacrylic, propylacrylic, etc., and arylacrylic such asphenylacrylic), crotonic, oleic, linoleic and linolenic; (c) polybasicacids such as oxalic, malonic, succinic, glutaric, adipic, pimelic,suberic, azelaic and sebacic; (d) unsaturated polybasic acids such asmaleic, fumaric, citraconic, mesaconic, itaconic, methylenemalonic,acetylenedicarboxylic and aconitic; (e) aromatic acids, e.g., benzoic,phenylacetic, phthalic, terephthalic and benzoylphthalic acids.

2. Esters of saturated alcohols, such as methyl, ethyl, propyl,isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, 2-ethylhexyl,cyclohexyl or behenyl alcohols, with unsaturated aliphatic monobasic andpolybasic acids, examples of which are illustrated above.

3. Esters of unsaturated polyhydric alcohols, e.g., butenediol, withsaturated and unsaturated aliphatic and aromatic, monobasic andpolybasic acids, illustrative examples of which appear above.

4. Vinyl cyclic compounds including (a) monovinyl aromatic hydrocarbons,e.g., allylbenzene, styrene, o-, m-, p-chlorostyrenes, -bromostyrenes,-fluorostyrenes, -methylstyrenes, -ethylstyrenes, -cyanostyrenes; di-,

' tri-, and tetra-, etc., -chlorostyrenes, -bromostyrenes,

-fluorostyrenes, -methylstyrenes, -ethylstyrenes, -cyanostyrenes;vinylnaphthalene, vinylcyclohexane; (b) corresponding polyvinylcompounds such as divinylbenzene and trivinylbenzene; and (c) vinylheterocycles such as vinylfuran, vinylpyridine, vinylbenzofuran,N-vinylcarbazole, N-vinylpyrrolidone, N-vinylthiopyrrolidone andN-vinyloxazolidone.

5. Unsaturated ethers such as methyl vinyl ether, ethyl vinyl ether,cyclohexyl vinyl ether, octyl vinyl ether, diallyl ether, ethylmethallyl ether and allyl ethyl ether.

6. Unsaturated ketones, e.g., methyl vinyl ketone and ethyl vinylketone.

7. Unsaturated amides, such as acrylamide, methacrylamide,N-methylacrylamide, N-phenylacrylamide, N-allylacrylamide,N-methylolacrylamide, N- allylcaprolactam, diacetone acrylamide and N-(1,1- dimethyl-3-hydroxybutyl)acrylamide.

8. Unsaturated aliphatic hydrocarbons, for instance, ethylene,propylene, butenes, butadiene, isoprene, 2- chlorobutadiene andalpha-olefins in general.

9. Vinyl halides, e.g., vinyl fluoride, vinyl chloride, vinyl bromide,vinylidene chloride, vinylidene bromide, allyl chloride and allylbromide.

10. Unsaturated acids (for example, acrylic, methacrylic,propylacrylic), examples of which appear above.

11. Unsaturated acid anhydrides, e.g., maleic, citraconic, itaconic,cis-4-cyclohexene-1,Z-dicarboxylic andbicyclo(2,2,1)-5-heptene-2,3-dicarboxylic anhydrides.

12. Unsaturated acid halides such as cinnamoyl, acrylyl, methacrylyl,crotonyl, oleyl and fumaryl chlorides or bromides.

13. Unsaturated nitriles, e.g., acrylonitrile, methacrylonitrile andother substituted acrylonitriles.

The preferred comonomers are vinyl esters of carboxylic acids,illustrated by vinyl acetate; alkyl esters of unsaturated carboxylicacids, illustrated by ethyl acrylate, 2-ethylhexylacry1ate and methylmethacrylate; unsaturated nitriles such as acrylonitrile; andunsaturated amides such as acrylamide, N-methylacrylamide andmethacrylamide.

The relative proportions of the compounds of this invention and thecomonomers to be used in interpolymerization depend upon the reactivityof these monomers as well as the properties desired for theinterpolymers being formed. To illustrate, interpolymers in whichrigidity is desired are obtained by polymerization of a mixture ofmonomers having a few substitutions or substitutions of relatively shortchain length. If a still higher degree of rigidity is desired, a monomermixture may be used in which a small amount of a bifunctional monomer isincluded such as divinylbenzene which will crosslink the polymer.

The polymers of this invention can also be prepared from polymers ofN-3-oxohydrocarbon-substituted acrylamides such as N-( 1,1-dimethyl-3-EXAMPLE 18 A solution of 10 parts ofN-(l,l-dimethyl-3-dimethylaminobutyl)acrylamide in 40 parts of benzeneis flushed with nitrogen for 10 minutes, and 0.05 part of benzoylperoxide is added. The solution is heated at 60-65C. for 16 hours, afterwhich an additional 0.05 part of benzoyl peroxide is added. Heating iscontinued for 16 hours, after which the benzene is removed byevaporation, leaving a viscous oil. This oil is dissolved in methanoland the solution is poured into water. The desired homopolymer of N-1,1-dimethyl-3-dimethylaminobutyl)acrylamide precipitates and is airdried.

EXAMPLE 19 Four grams (0.202 mole, based on monomer) of the polymer ofExample 18 is dissolved in 25 m1. of methanol and 2.85 grams (0.202mole) of methyl iodide is added. The solution is heated at 50-60C. for 1/2 hours, during which time a white precipitate forms. The liquid isremoved by decantation and the precipitate, which is the desiredpoly-[trimethyl-3-(l-acrylamido- 1,l-dimethylbutyl)ammonium iodide], iswashed with acetone and air dried.

EXAMPLE 20 A mixture of 20 parts ofN-(1,1-dimethyl-3-dimethylaminobutyl)acrylamide, parts of water and 0.1part of sodium lauryl sulfate is purged with nitrogen for one-half hour,and then a solution of 0.1 part of ammonium persulfate in one part ofwater is added. The solution is stirred as polymerization takes place.The mixture is allowed to stand overnight and is then filtered. Thedesired suspension homopolymer is air dried.

EXAMPLE 21 A solution of 20 parts (0.109 mole) of N-( 1,1-dimethyl-3-dirnethylaminopropy1)acrylamide in 8.5 parts of water ispurged with nitrogen and 0.5 part of ammonium persulfate is added. Themixture is stirred for about 1 /2 hours, during which timepolymerization takes place. Water, parts, is then added followed by 13.7parts (0.109 mole) of dimethyl sulfate. An exothermic reaction takesplace as stirring is continued overnight. There is obtained an aqueoussolution of the quaternized homopolymer from which water is removed byevaporation and vacuum drying.

EXAMPLE 22 The procedure of Example 18 is repeated, except that themonomer is replaced on an equal weight basis with N-( 1,3-diphenyl-1-methyl-3-dimethylaminopropyl)acrylamide. A similarhomopolymer is obtained.

EXAMPLE 23 The procedure of Example 18 is repeated, except that themonomer is replaced on an equal weight basis by N-(l,1-dimethyl-3-methylanilinobutyl)acrylamide. A similar homopolymer isobtained.

EXAMPLE 24 To a solution of one part of N-(l,l-dimethyl-3-dimethylaminobutyl)acrylamide in 5 parts of water isadded 0.1 part of methylene blue and a solution of 0.2 part oftriethanolamine in parts of water. The solution is exposed to aninfrared heat lamp, and polymerization begins after about 3 seconds asevidenced by the dissipation of blue color in the solution and theformation of a hazy precipitate.

EXAMPLES 25-27 Copolymers of acrylonitrile with N-( l,l-dimethyl-3-dimethylaminobutyl)acrylamide are prepared, respectively, from 49.5parts of acrylonitrile and 0.5 parts of the acrylamide, 47.5 parts ofacrylonitrile and 2.5 parts of the acrylamide, and 45 parts ofacrylonitrile and 5 parts of the acrylamide. In each case, thepolymerization is effected by dissolving the monomers in 600 parts ofwater, flushing with nitrogen and adding a solution of 0.25 part ofammonium persulfate in 1 part of water. When precipitation of thecopolymer is complete, it is removed by filtration, washed with waterand dried in a vacuum oven.

EXAMPLE 28 Dimethyl sulfate, 2.03 parts, is added to a solution of 2.97parts of N-(1,l-dimethy1-3-dimethylaminopropyl- )acrylamide in 225 partsof water, with stirring. An exothermic reaction takes place over aboutone-half hour. Acrylamide, parts, is then added and the solution ispurged with nitrogen, after which time about 0.5 gram of ammoniumpersulfate is added. Polymerization takes place over 4 hours, and afterthis time 200 parts of water is added and stirring is continued. Ahomogenous mixture is obtained which is diluted with water to a 1%solution of the desired quaternized copolymer.

EXAMPLE 29 A mixture of 40 parts of vinyl acetate, 10 parts of N-(1,l-dimethyl3-dimethylaminobutyl)acrylamide, 0.5 part of sodium laurylsulfate and 450 parts of distilled water is flushed with nitrogen, and asolution of 0.25 part of ammonium persulfate in 1 part of water isadded. The mixture is heated to 55C., with stirring, and is held at thistemperature for 1 hour. The product is an emulsion of the desiredcopolymer.

EXAMPLE 30 Following the procedure of Examples 25-27, a copolymer isprepared from 30 parts of ethyl acrylate, parts ofN(1,l-dimethyl-3-dimethylaminobutyl)acrylamide, 450 parts of water, 0.5part of sodium lauryl sulfate and a solution of 0.25 part of ammoniumpersulfate in 1 part of water. The polymer which is obtained bycoagulation is filtered and dried in a vacuum oven.

Incorporation of the acrylamido compounds of this invention inacrylonitrile polymers improves their dyeability. This is shown by atest in which films of the copolymers of Examples -27 are compared witha polyacrylonitrile film in reaction to Orange 11 dye. The films aresuspended for 1 /2 hours in a 0.05% aqueous solution of Orange 11 at8098C., washed with distilled water and dried. Followingthis procedure,the poly acrylonitrile film is uncolored while the color in the films ofExamples 25-27 increases in proportion to the amount of N-(l,l-dimethyl-3-dimethylaminobutyl )acrylamide incorporated therein.

The dyeability of polypropylene is also improved by treatment with thepolymers of this invention. This is shown by a test in which 2.5 grams,5.0 grams and 7.5 grams, respectively, of an N-(1,1-dimethyl-3-dimethylaminobutyl)acrylamide homopolymer similar to thatof Example 20 are added to 50-gram samples of polypropylene. Sufficientmethanol is added to cover the polypropylene and the mixtures are shakenfor 1 minute and allowed to stand in closed bottles for 40 minutes. Thebottles are then opened and the methanol is removed by evaporation atroom temperature and finally in a vacuum oven at 4850C. Films of the resulting modified polypropylene samples are suspended in the Orange 11dye solution described above at 6090C. for 2% hours. The strips are thenremoved, rinsed with distilled water and dried. Each of the strips isnoticeably colored by the dye.

The polymers of this invention are useful to improve both dry strengthand wet strength of paper. Their utility as dry strength improvers isshown by a test in which strips of filter paper are saturated with a 5%solution in methanol of the polymer of Example 20 and dried bysuspension for 2 hours at room temperature. The average tensile strengthof the treated strips, as measured on an Instron tester using acrosshead speed of 0.2 inch per minute at a temperature of 72F., was21.6 pounds per inch width, as compared with 13.8 pounds per inch widthfor untreated specimens.

Quaternized polymers of this invention are useful as flocculants forprecipitation of many substances from water. The effectiveness of thesepolymers as flocculants for the precipitation of kaolin is shown by atest in which one part of kaolin is suspended in parts of water andabout 0.1 part of a 20% aqueous solution of the polymer of Example 19 isadded. The suspension is shaken for about one-half minute and allowed tostand. A flocculent precipitate forms immediately. By contrast, thekaolin in a control sample which is not treated with homopolymer ofExample 19 remains sus pended.

Flocculant Concentration, ppm. Turbidity Homopolymer of Ex. 21 l 2.57 22.03 4 0.931 8 0.400 10 0.152 12 0.112 13 0.090

Copolymer of Ex. 28 l 1.39

The monomers of this invention, by virtue of their susceptibility tophotoinitiated polymerization, are useful in photo-engraving andphotographic techniques. They may also be copolymerized withcrosslinking agents such as divinylbenzene, in the presence ofsuspending agents such as bentonite, to form cationic ion exchangeresins.

What is claimed is:

1. A polymer of a compound of the formula RSRSH R7 wherein each of R, Rand R is hydrogen or a hydrocarbon radical; each of R and R is ahydrocarbon radical; R is hydrogen or a lower alkyl radical; X is asaltforming anion; each of Z and Z is a lower alkyl or C cycloalkylradical, or

. polymer.

5. A polymer according to claim 3 which is an interpolymer of saidcompound with at least one polymerizable unsaturated monomer.

6. An interpolymer according to claim 5 wherein the polymerizableunsaturated monomer is a vinyl ester of a carboxylic acid, an alkylester of an unsaturated carboxylic acid, an unsaturated nitrile, or anunsaturated amide.

7. An interpolymer according to claim 6 which is a copolymer of saidcompound with acrylonitrile or methacrylonitrile.

8. A copolymer according'to claim 7 wherein R is hydrogen or methyl; R Rand R are hydrogen; R and R are methyl; and each of Z, Z and Z ismethyl.

1. A POLYMER OF A COMPOUND OF THE FORMULA
 2. A polymer according toclaim 1 wherein R7 is hydrogen or methyl.
 3. A polymer according toclaim 2 wherein each of R1, R2 and R3 is hydrogen or a lower alkylradical, each of R4 and R5 is a lower alkyl radical, R7 is hydrogen, andeach of Z1 and Z2 is a lower alkyl radical.
 4. A polymer according toclaim 3 which is a homopolymer.
 5. A polymer according to claim 3 whichis an interpolymer of said compound with at least one polymerizableunsaturated monomer.
 6. An interpolymer according to claim 5 wherein thepolymerizable unsaturated monomer is a vinyl ester of a carboxylic acid,an alkyl ester of an unsaturated carboxylic acid, an unsaturatednitrile, or an unsaturated amide.
 7. An interpolymer according to claim6 which is a copolymer of said compound with acrylonitrile ormethacrylonitrile.
 8. A copolymer according to claim 7 wherein R1 ishydrogen or methyl; R2, R3 and R7 are hydrogen; R4 and R5 are methyl;and each of Z1, Z2 and Z3 is methyl.